Production of resins from aldehydes and aromatic hydrocarbons



Patented may lid, Wdfl UNITED STNiEfl ears- PRODUCTION OF RESINS FRGM ALBE- HYDES AND AROMATIC HYDROGARWUNfi No Drawing. Application June 20, 1038, Serial No. 216,469

id Claims.

This invention relates to hydrocarbon resins produced by polymerization of the condensation product of an aldehyde and an aromatic hydrocarbon.

; The condensation of aromatic hydrocarbons with aldehydes, as well as the production of resins by polymerization of the product, has been known for many years, and much work has been done along these lines. The classical catalyst,

l and that generally used, which serves both as a condensing agent and as polymerizing stimulus is concentrated (66 B.) sulfuric acid. Its use for simple condensation purposes may be unobjectionable, but in efiecting polymerization l disadvantageous results appear which militate against its successful use in the commercial production of resins of this class. For instance, the use of ordinary concentrated sulfuric acid is generally accompanied by the formation of very- I ing amounts of insoluble and infusible resins, which is objectionable because for many of the more important uses of these resins the quality of solubility is essential. Similarly, the infusibility oi the resin precludes its use for some puri poses.

In general these reactions are effected at moderately elevated temperatures, say 60 to 180 (3., which favors side reactions such as oxidation and. sulfonation, caused by the sulfuric acid. Not only do these undesired reactions reduce the resin yields, but also they tend to cause the resin to be of a dark color and consequently of depreciated commercial value. The use of ordinary concentrated sulfuric acid is objectionable also because the resin as recovered carries small amounts of acid which must be removed by treatment with alkali. Commonly the procedure is to extract the reaction mixture with an aromatic solvent, such as xylol, and then neutralize the solution with an aqueous solution of caustic soda. Due to the presence of dissolved and dispersed high molecular weight products and sulfonated compounds, highly stable emulsions are formed which can be broken only by prolonged heating at, for instance, 90 to 95 C. The finished resin always contains some dispersed salts and alkali, which is objectionable, andsome amount of resin may be lost through imperfect resolution of the emulsion into its component parts. i

All of these factors increase the cost of the resin. Costs are further increased because large volumes of solvent may be necessary in extracting the resin from the reaction mixture (as much as 9 volumes of xylol may be required to the distillation of such is an additional unproeiiect extracti n) and large excess of solvent ductlve expense.

These undesirable consequences arise, as noted, from the tendency of ordinary concentrated sulfuric acid to cause oxidation and sulionation, either or both, of the reaction ingredients or their products. ,It might be thought that these side reactions might be repressed by dilution of the acid with water, but this is not the case because water-diluted sulfuric acid will not satisfactorily effect the desired resin-forming reactions.

It is among the objects of the invention to provide a method of making hydrocarbon resins of the type to which reference has been made which is simple, easily performed, and readily controlled, and in which the disadvantages heretofore encountered in the use of concentrated sulfuric acid are repressed or eliminated.

The invention is predicated upon our discovery that the condensation of an aldehyde and an aromatic hydrocarbon with polymerization of the product may be effected satisfactorily and without the disadvantages attendant upon the use of ordinary concentrated sulfuric acid, by subjecting the reaction mixture to the condensation and polymerization stimulus of a modified sulfuric acid catalyst selected from the group mixtures and heat promoted reaction products of alkyl ethers and concentrated sulfuric acid. Such catalysts, we have found, have less omdizing and sulfonating efiect upon the reaction mixture and its products than ordinary unmodified sulfuric acid, while their emcacy in de hydrating and polymerizing is unimpaired. We have found that by the use of such a catalyst there are obtained satisfactory yields of light colored resins, the production of insoluble polymers is minimized, and no appreciable oxidation or sulfonation, with their attendant disadvantages, occurs. Moreover, the resin may be separated more readily, quickly and cheaply from the spent catalyst than from the residue of ordinary concentrated sulfuric acid, and the entire procedure is simplified, shortened and cheape'ned.

The invention is applicable generally to aldehydes and aromatic hydrocarbons. For instance, there may be used formaldehyde, acetatdehyde, and other aliphatic aldehydes, which generally are preferred, although the various aromatic aldehydes, exemplified by benzaldehyde, may be used. This condensation is applicable, as far as we are aware, generally to aromatic hydrocarbons. By way of illustratilt tit

tion and not of limitation, the aldehyde may be condensed with such widely varying aromatic hydrocarbons as benzene, toluene, xylene, naphthalene, phenanthrene, acenaphthene, mesitylene, diphenyl, and many others. Not only is it applicable to the pure hydrocarbons, but also to mixtures of hydrocarbons. The applicability of the reaction to such mixtures is exemplified by the condensation of solvent naphthas which have been freed, or substantially freed, from unsaturated bodies and which consists chiefly of homologs of benzene, and by the condensation.

of the heavy oils resulting from the polymerizatlon of such hydrocarbons as indene and which largely comprise the dimers and trimers with perhaps some indene monomer.

The resins produced by the invention are characterized, in general, by possessing thermoplastic properties, by stability to heat up to temperatures at which they crack or decompose, by solubility in hydrocarbon solvents, and by insolubility in alcohols.

mixtures of concentrated sulfuric acid with an' alkyl ether. Preferably we use the saturated others from and including diethyl ether to diamyl ether, and most suitably isopropyl ether.

Although the exact proportions in which the acid and ether are mixed are not critical, as long as enough ether is present to repress oxidation and sulfonation, the best results are'had by using an excess of ether although the fluse of too great an excess imports the cost of distillation after the reaction has been completed. As an example, we have found that in the case of isopropyl ether a suitable proportion is from 4 to 5 volumes of ether per volume of acid. Such-.ether-acid mixtures should preferably be used before they l have stood for any great length of time.

While we do not bind ourselves to this theory f we now believe that when the sulfuric acid diluted with ether the two react to form some amount of an alkyl sulfuric acid catalyst which serves to initiate thereactions, and that this reaction between the ether and acid progresses, to form further amounts of catalyst, underthe heat used in the condensation and polymerization. Be this as it may, we have found'that an allwl sulfuric acid catalyst produced by intentional reaction of ether and acid, such as an alkyl acid sulfate, may be used satisfactorily in the practice of the invention and with advantage, eco-' nomically, as compared with simple mixtures of ether and acid such as those to which reference has just been made}. For this purpose we prefer to use the ethers described hereinabove, especially diethyl ether and particularly isopropyl ether. In practicing this embodiment of the invention the ether and acid are mixed in suitable proportions and then heated gently, say at 50 to 75 0., most suitably at 50 to 60 C., for a Also, as noted,'the prac-' tice of the invention yields light colored resins.

sufficient period pf time to cause the reaction to reach equilibrium with production of alkyl sulfuric acid catalyst.

For most purposes there should be used at least 1 mol, and preferably more than 1 mol, of acid for each mol of ether, and we believe that in general it is desirable to use up to about 2 mols of acid for each mol of ether, although for reasons of economy it is preferred to use not more than slightly in excess of the latter proportions. The reason for this is that there is an increase in utilization of ether to form stable alkyl sulfuric acid compound as the excess of acid is increased up to about 1 mol ofacid pert 035 mol of ether,

or slightly less, say 0.493 ,mof bf ether. In the practice of the invention the aldehyde and hydrocarbon are mixed,- the catalyst is added,

and the reaction is then carried out. Moderate- 1y elevated temperatures are generally necessary, but the precise temperature will depend, at least in part, upon the particular catalyst, aldehyde and hydrocarbon involved, and upon the character, e. g., the melting point, desired in the resin. Hence specific temperature limits can not be given for all possible conditions, but the temperature should be high enough to cause the reactions-to proceed satisfactorily, and low enough to avoid cracking of the resin. It may be stated, however, that as low temperatures as possible should be used to avoid undesirable darkening of the resin.' As an example, using formaldehyde temperatures of about to 135 C. suffice for many purposes. The reaction mixture is preferably agitated vigorously during the course of the reaction. When the reaction has reached completion the resin may be recovered in simple manner by various procedures some of which are exemplified in the examples presently to be given.

The proportions in which the aldehyde and hy- Generally speaking, however, the yield of resin and its hardness improve as the proportion of aldehyde increases. We believe that for most purposes the use of 1 to 2 mols of aldehyde, such asformaldehyde, per mol of aromatic hydrocarbon affords satisfactoryresults.

The following examples are illustrative of the invention and its benefits. s

i In one test the catalyst was made by mixing 17.2 grams of 66 sulfuric acid with 2'7 grams of isopropyl ether. This catalyst was added in batches during a five-minute interval to a mixture of 319 grams of xylol (industrial grade) and 42.5 grams of ,trioxymethylene in a reaction vessel provided with a stirrer and a reflux condenser adapted to prevent condensed water from returning to the"vessel.- The mixture was stirred continuously up to theend of the reaction. The first addition caused the temperature to rise from 20 to 26 C., but there was no further temperature increase, showing the excellent manner in which the character of the sulfuric acid hrs been modified. When all of the catalyst had been added the contents of the vessel were heated three hours at 100 to 1&0 C. There was then added an equal weight. of petroleum benzine which caused theQformationof two layers. The acid layer was withdrawn,jand'to the resin solution 21.5 grams of Attapulgus clay were added to clean up traces of acid. The mixture was heated 30 minutes atf .to C. and filtered. The petroleum benzine was distilled from the filtrate at atmospheric pressure, and the residue was steam distilled to remove oils from the resin. There resulted 122.5 grams of resin of 78 C. melting point and a color of 3 on the Neville Company color scale. A 20 per cent by weight solution of this resin in Stoddard naphtha was stable below 15 C. The distillate comprised 73.7 grams of heavy oil.

In another test 8. adding 80 gallons of slowly to 106 gallons catalyst was prepared by sulfuric acid (66 acid) of isopropyl ether. The

mixture was stirred and was kept below 40 C.

mixture was heated It was then diluted with 500 cc. of Stoddard The temperature was then raised to 50 to 60 0. and held in this range for threehours and then cooled to room temperature. used in this test a high flash naphtha boiling at 160 to 185 C. and having a specific gravity of 0.875 at 15.5/15.5 C. To 240 grams of this naphthe and 60 grams of trioxymethylene contained in a reaction vessel added 22 grains of the foregoing catalyst. The three hours at 90 to 100? C.

naphtha and 16 grams each of Attapulgus clay and of Superfiltrol clay were added, the mixture heing then heated 1 hour at 110 filtration. The filtrate at room temperature;

a distillate oil which solidified on t 108 grams of resin of 06 C. melting point, and v bi4color. Y i m As further exemplifying the applicability of the invention, of 66 sulfuric acid to 26.4 ml.

and 102.9 grams ant contained in ceding example.

for a total period of live the contents were at 100 to112 C. for four hours.

The resinwas recovered by adding an equal 3 1 weight of petroleum benzine and 64.5 grams of activated clay, and heating to 95 to 102 C..ior 30 minutes. The resin at 100 to 108 C. After filtering from the clay the filtrate was distilled as before, producing 158.2 grams of dinaphthyl'methane resin of 116 C. melting point and a"color of 2.5. The distillate comprised 9.4 'grarns of heavy oil and 20 grams of unreactednaphthalene. i

In yet another test there were .used2 32, grams of Nevinol, 120 grams of thesolvent and 15 grams of trioxymethylene. naphthahad a boiling rangeirom naphtha,

which is the oil remainingaiter No. vent naphtha has been freed of The catalyst wasta mixtureof 18.4

2 crude solunsaturates.

the mixture in a container as before, with a to tal tem'perature rise of but 34C. The mixture was then heated four hours and thirty-five minutes at 100 to 150 (1, and was then treated in the manner of the first example. This produced 191.9 grams of asoit resin of about 10C. M. P., and with a color of 4. Theheavy oil appeared to be unreacted Nevino1" iOId by the Neville Company, Pittsburgh,='Pa-.' It. the polymerization of solvent naphtha, and

s a heavy oil obtained in ;he unsaturates in crude There was as described above there were i (3., followed by naphtha was distilled from the i the residue was steam distilled two hours at 250 C., producing); cooling, and a a catalyst madeby adding 6.6 ml. of isopropyl ether was added slowly to 197.1 grams of naphthalene C. M. P.) 46.2 grams of trioxymethylene,

petroleum benzine as a dilu-y a reaction vessel as, in theior'e- No temperature rise occurred] during the addition of the catalyst- Thecontents oi the vessel were heated and agitated" hours during whichtime l ch involved ,Q-being isopropyl ether.

.heing "isopropyl' ether and the was extracted with lol xy :comprisingabout 4 volumes of step which The solvent i which is a product i it is composed largely of the dimers and trimers of coumarone and of indene.

According to the provisions of the patent statutes, we have explained the principle of our invention and have described what we new consider to represent its best embodiment. However, we desire to have it understood that, within the scope of the appended claims, the invention may be practiced otherwise than as specifically described.

We claim:

1. In a method of making resin by reaction of an aldehyde upon an aromatic hydrocarbon, the

step which comprises subjecting a mixture oi an aldehyde and an aromatic hydrocarbon to the 'condensing and polymerizing influence of a catalyst selected from the group consisting of mintures and reaction products of alkyl ethers and concentrated sulfuric acid, said ethers being not chemically involved in said condensation and "polymerization.

2.A method according to claim 1, said ether being isopropyl' ether. 3. That method of subjecting a mixture 'ductive" of condensation of said aldehyde and hydrocarbon and recovering polymerized condenilyst comprising a mixture of an alkyl ether and concentratedsulfuric acid, said ethers being not in said condensation and polymerization.

, 5. A method according to claim a, said ether .A'm'ethod accordingto claim 4, said ether catalyst mixture ether per volume 30f acid. v 7. Inla lnethod of making resin by reaction of an aldehyde. upon an aromatic hydrocarbon, the

being isopropyl ether.

10. In a method "of making resin by reaction of an aldehyde upon an aromatic hydrocarbon,

thestep which comprises subjecting a mixture of an aldehyde and an aromatic between isopropyl ether and concentrated sulfuric acid 10. A method according to claim 9, said acid and ether being reacted in proportions approximating mols of acid per mol of ether.

11. In a method of making resin by reaction of formaldehyde upon an aromatic hydrocarbon, the step which comprises subjecting a mixture of formaldehyde and an aromatic hydrocarbon to the condensing and polymerizing influence of a catalyst comprising a mixture of isopropyl ether and concentrated sulfuric acid, said ethers being not chemically involved in said condensation and polymerization.

12. A method according to claim 11, the reaction being effected at 90 to 135 C.

13. In a method of making resin by reaction of formaldehyde upon an aromatic hydrocarbon,

the step which combrises subjectinga mixture vof formaldehyde and an aromatic hydrocarbon to the condensing and polymerizing influence of a catalyst produced by heat promoted reaction of isopropyl ether and concentrated sulfuric acid in proportions from more than 1 to slightly more than 2 mols of acid per mol of ether, said ethers being not chemically involved in said condensation and polymerization.

14. A method according to claim 13, the treatmerit of the aldehyde and hydrocarbon being 10 efiected at about 90 to 135 C.

GEORGE K. ANDERSON. EDWARD A. TAYLOR. JOHN B. FISHEL. 

